CEMENT AND LIME Chemical Process Technology CHE C322

INDIAN CEMENT INDUSTRY

India, being the second largest cement producer in the world after

China with a total capacity of 210 Million Tones (MT)[*based on USGS Mineral Program Cement Report, Jan 2012]. The cement industry in India is dominated by around 20 companies, which account for almost 70% of the total cement production in India. Following are the list of top 10 cement companies in India:
ACC Limited Ambuja Cements Limited UltraTech Cement Limited India Cement Limited Shree Cement Limited

Prism Cement Limited Madras Cement Limite Birla Cement Limited JK Cement Limited

Rain Cement Limited

cement
Cement : It is the generic name for powdered materials which initially have plastic flow when mixed with water or other liquid, but forms a solid structure in several hours with varying degree of strength and bonding properties which continues to improve with age. Constituents of cement
Chemical formula 2CaO.SiO2 3CaO.SiO2 3CaO.Al2O3 4CaO.Al2O3.Fe2O3 Ca(OH)2 Type Silicate Code C2S C3S Aluminate C3A C4AF Hydroxide Property Provides strength High heat of hydration Superior resistance to sea and sulfate water Low strength

types of cement
Depending on the type of constituent the cement can be classified as 1. Portland Major having silicates, eg. C2S; C3S 2. High alumina Major having aluminates , C3A, C4AF 3. Hydraulic hydrated lime Hydroxide, Ca(OH)2

Also cement is characterized on various other factors such as: strength, heat evolution, rate of setting.
Rapid-hardening cement is used in precast concrete, pipes and tiles. It is

finer ground so that it hydrates more quickly and has more gypsum than other cements. Moderate-heat cement is used for the construction of hydro-electric dams, as the heat produced by ordinary cement creates uneven expansion and hence cracking when such a large volume of concrete is used.

METHODS OF PRODUCTION
Most common type is Portland cement. The method of production of cement from lime

rock can be done in two steps1. Cement rock beneficiation- Mostly based on use of the local limestone rock with high silica and iron content. 2. Portland cement production- chemical reactions limestone and other constituents.

PORTLAND CEMENT PROCESS

Raw material

Limestone (70-80% rich in CaCO3) Clay (15-20% , a source of silica, alumina and Fe2O3) Other : gypsum, coal, water.
Chemical reaction

CaCO3 CaO + CO2 (1000 oC) CaO + Al2O3 + SiO2 Mixtures of C3S , C2S, C3A Process Type Dry Process: uses more energy in grinding but less in the kiln Wet Process has lower overheads than the dry process

Limestone Beneficiation
If available limestone has too high a silica and iron content and undesired constituent, these are removed by ore dressing or beneficiation methods. Grinding Classification Flotation Thickening

[1] Raw material preparation

Dry Process: Quarried clay and limestone are crushed separately and then fed together into a mill where the rock is ground until more than 85% of the material is less than 90m in diameter. Wet process: The clay is mixed to a paste in a washmill - a tank in which the clay is pulverised in the presence of water. Crushed lime is then added and the whole mixture to further ground.

[2] Clinkering
The finely ground material is dried, heated (to enable the sintering

reactions to take place) and then cooled down again. While it is being heated various chemical reactions take place to form the major mineral constituents of Portland cement.

The powder from the dry process doesn't contain much moisture, so

can be dried in a preheater. The slurry from the wet process contains too much moisture to be successfully dried in a preheater tower. Instead, the slurry is fed directly into the kiln where it is formed into dry balls by the heat and rotation of the kiln. Because of this extra role of the kiln, wet process kilns are generally longer (100 m) than dry process kilns (60 m long). The kilns used in both processes are inclined on a shallow angle and lined with heat-resistant bricks.

KILN

The kiln is heated by injecting pulverized coal dust into the discharge end where it spontaneously ignites due to the very high temperatures. Zone 1: 0 - 35 min, 150-800 - oC Dehydration in wet process (in dry process preheating removes water) Zone 2: 35 - 40 min, 900 - 1300oC Decarbonation. Formation of 3CaOAl2O3,Melting of fluxing compounds Al2O3 and Fe2O3. Exothermic reactions and the formation of secondary silicate phases Zone 3: 40 - 50 min, 1300 - 1450 - 1300oC Sintering and reaction within the melt to form ternary silicates and tetracalcium aluminoferrates: Zone 4: 50 - 60 min, 1300 - 1000oC Cooling and crystallization of the various mineral phases formed in the kiln.

Inclination :3 -4 degrees Rotation :1.2-2 rpm

[3] Cooling Immediately following the kiln is a large cooler designed to drop the temperature of the clinker (as the fused material is now called) from 1000oC to 150oC. This is achieved by forcing air through a bed of clinker via perforated plates in the base of the cooler. The plates within the cooler slide back and forth, shuffling the clinker down the cooler to the discharge point and transport to a storage area. [4] Cement Milling To produce the final product the clinker is mixed with gypsum (CaSO4 2H2O), which is added as a set retarder, and ground for approximately 30 minutes in large tube mills. The cement flows from the inlet to the outlet of the mill (a rotating chamber), being first ground with 60 mm then 30 mm diameter steel balls. The first grinding breaks up the material and the second grinds it to a fine powder.

Process Flow sheet

Major Engineering Problems

Type of grinding
Wet or dry grinding (dry grinding being used in most new plants). Emphasis on good design as 80% of total power consumed in crushing,

grinding and blending.

Kiln Design
Calcining, concreting requires heat for water evaporation, oxidizing

organic material, volatilization. Wet process requires 90-170 m length kiln, dry process kilns may be as short as 50 m.
Heat Economy
Balance between fuel cost and addition of waste heat boiler and air

preheater. Heat requirement for wet grinding process1,300-1800 Kcal/kg and 7001000 for dry grinding process.

 Quality Control
Product performance is sensitive to rock composition, particle size,

and degree of calcining. Instrumentation and control of kiln has proven quality improve.
Economics of Cement Industry
In view of ecological and economic aspects, nowadays, Portland

cement components are increasingly substituted by e.g. blast-furnace slags, puzzolana, fly ashes or lime stone powders. CaCO3 from fertilizer (as sludge) can be used Thus, the cement can be optimally tailored to the requirements on the construction site. And, there is more to it than that: Carbon dioxide emissions are reduced, too.

Cement Kiln
Geetansh Gupta Apoorv Bhardwaj

Introduction
Used in the pyro processing stage of manufacture of Portland

& types of hydraulic cement. Main energy-consumption and greenhouse-gas emission stage. Improvement of kiln efficiency has been the central concern of cement manufacturing technology. Types of Cement Kilns
Shaft Kilns Briefly used from 1970. Still in use in low-tech

plants. Rotary Kilns Currently in use. Accounts for 95% of global production.

The Shaft Kiln

The Rotary Kiln

Consists of a steel tube, lined with firebrick. Tube slopes at (1-4o) and slowly rotates on its axis between

30 and 250 rev/h. Rawmix is fed from the upper end. The lower end of the tube has a large concentric flame.

Methods of Rawmix Preparation

Two different methods of rawmix preparation are used:
Dry Process - Mineral components are dry-ground to a form a powder. Wet Process - Water is added to the mineral components to produce a slurry with 4050% water content.

Comparison:
Dry process saves on extra fuel needed for water evaporation. In dry process, no kiln length is used up in drying rawmix. It is difficult to keep the dry powdered rawmix in kiln due to

fast flowing combustion gases, hence spray water is used. Granulation is more difficult in dry process.

Different zones and temperature profile

Successive chemical reactions take place as the temperature

of the raw mix rises: 70 to 110 C - Free water is evaporated. 400 to 600 C - clay-like minerals are decomposed into their constituent oxides; principally SiO2 and Al2O3. Dolomite (CaMg(CO3)2) decomposes to calcium carbonate, MgO and CO2. 650 to 900 C - calcium carbonate reacts with SiO2 to form belite(Ca2SiO4). 900 to 1050 C - the remaining calcium carbonate decomposes to calcium oxide and CO2. 1300 to 1450 C - partial (2030%) melting takes place, and belite reacts with calcium oxide to form alite (Ca3OSiO4).

LIME
LIME refers to Limestone (CaCO3) and its derivative burnt/quick lime (CaO) and slaked/hydrated lime (Ca(OH)2). Physical properties CaO ( Quick lime) Ca(OH)2 ( Slaked lime) Mol. Wt 56.08 Mol. Wt 74.10 M.P 2570 oC Density 2.2 g /cm3 B.P 2850 oC Decomposes to CaO at 580oC Density 3.32 g / cm3 Soluble in water and acids Slightly soluble in water,
Uses: Burnt and hydrated lime are used in many industries to neutralize

acid waste, and are used as causticisers in the pulp and paper industry and as flux in the steel industry.

LIME
Methods of production
Quick lime Calcining limestone to yield quicklime Slaked Lime Hydration of quicklime

Write the reactions, temperature, (exo/endothermic) Based on above information and process discussed for

cement production, draw a conceptual block diagram (combined) for Quick and Slaked Lime.

Method of production
Quick lime
Calcining limestone to yield quicklime

CaCO3 (s) CaO (s) + CO2 (g) H =+44 kcal High quality limestone (>95% CaCO3) is calcined in a continuous process using rotary or vertical kilns at (1000-1100oC), volatilizing off the carbon dioxide to leave the calcium oxide:

Slaked Lime
Hydration of quicklime

CaO(s) + H2O (l or V) Ca(OH)2 It is produced by reacting burnt lime with water in a continuous hydrator. During this process large amounts of heat are given off. The resultant micron-sized particles are then classified by air separators which reject coarse particles.

The basic processes in the production of lime are: Quick Lime (1) Quarrying raw limestone (2) Preparing limestone for the kilns by crushing and sizing
Jaw or gyratory crushers for hard rock Hammer or roll mills for soft rock

Size of feed depends on calciner type.

(3) Calcining limestone Type Particle size

Vertical Shaft

10-20 cm Efficient for small production Rotary Kiln 0.5-5 cm Large production, better control Operation is of two type : Unmixed and mixed

(4) Cooling in conveyor and the lime is either packaged as Lump lime or crushed and screened to yield pulverized lime. Hydrated Lime (5) Processing the lime further by hydration
Quicklime lumps are crushed to 2 cm or less then added along with water or steam to a vertical

cylindrical pug mill. Product from complete reaction is light, dry slaked lime which is classified by screen or air separators to remove any unreactive lime.

Flow-sheet for CaO and Ca(OH)2

Major Engineering problems

1.

Choice of kiln

highest CO2 concentrations and good heat economy, higher fuel effciency. Rotary Kilns: Favored for large production rates, easy control over temperature and residence time, Beneficiated limestone slurry or precipitated calcium carbonate sludge cal also be handled. 2. Heat transfer operation Optimization of particle size, residence time, gas temperature, velocity profile and heat economy in kilns. 3. Economics of lime industry Very dependent on steel industry as lime use as slag removal (silica impurity) from iron. Energy intensive, as high temperature is required to make it from limestone.

Vertical Kilns: Suitable for smaller capacity type operations; yield

EMISSION FEATURES AND CONTROL MEASURES IN LIME PROCESS

Aaditya Shah Harshit Budholiya

LIME KILN
A lime kiln is used to produce quicklime through

the calcination of limestone (calcium carbonate).

The chemical equation for this reaction is

CaCO3 + heat CaO + CO2 a temperature around 1000C is usually used to make the reaction proceed quickly.

GAS CLEANING
All kiln designs produce exhaust gas that carries an

appreciable amount of dust. Lime dust is particularly corrosive. Equipment is installed to trap this dust, typically in the form of electrostatic precipitators or bag filters. The dust usually contains a high concentration of elements such as alkali metals, halogens and sulphur.

Carbon dioxide emission

The lime industry is a significant carbon dioxide emitter. The manufacture of one tonne of calcium oxide involves

decomposing calcium carbonate, with the formation of 785 kg of CO2 Additionally, if the heat supplied to form the lime (3.75 MJ/kg in an efficient kiln) is obtained by burning fossil fuel it will release CO2: in the case of coal fuel 295 kg/t; in the case of natural gas fuel 206 kg/t. Thus, total emission may be around 1 tonne of CO2 for every tonne of lime even in efficient industrial plants, but is typically 1.3 t/t.

EMISSION CONTROL
Carbon dioxide scrubber
A carbon dioxide scrubber is a device which

absorbs carbon dioxide (CO2). Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage.

Technologies
Sodium hydroxide Amine scrubbing Minerals and zeolites Lithium hydroxide Activated carbon

Sodium hydroxide
First, CO2 is absorbed by an alkaline NaOH solution to

produce dissolved sodium carbonate. The absorption reaction is a gas liquid reaction, strongly exothermic. 2NaOH(aq) + CO2(g) Na2CO3(aq) + H2O(l)

Na2CO3(aq) + Ca(OH)2(s) -> 2NaOH(aq) + CaCO3(s) [H = -5.3 kJ/mol]

 Subsequently, the calcium carbonate precipitate is filtered

from solution and thermally decomposed to produce gaseous CO2. The calcination reaction is the only endothermic reaction in the process. CaCO3(s) CaO(s) + CO2(g) H = + 179.2 kJ/mol Hydration of the lime (CaO) completes the cycle. CaO(s) + H2O(l) Ca(OH)2(s) H = -64.5 kJ/mol

Amine scrubbing

Virtually the only technology being seriously evaluated

involves the use of various amines, e.g. monoethanolamine. Cold solutions of these organic compounds bind CO2, but the binding is reversed at higher temperatures:

CO2+2HOCH2CH2NH2 <-->HOCH2CH2NH3+HOCH2CH2NH(CO2-)

This technology has only been lightly implemented because

of capital costs of installing the facility and the operating costs of utilizing it.

Activated carbon
Air with high carbon dioxide content, can be blown

through beds of activated carbon and the carbon dioxide will adsorb onto the activated carbon. Once the bed is saturated it must then be "regenerated" by blowing low carbon dioxide air, such as ambient air, through the bed. This will release the carbon dioxide from the bed, and it can then be used to scrub again, leaving the net amount of carbon dioxide in the air the same as when the process was started.